Process for obtaining nicotine carbolates from crude shale oil



June 10, 1930. v D. T, DA; 1,762,471

PROCESS FOR OBTAINING NICOTINE CARBOLATES FROM CRUDE SHALE OIL Filed Nov. 12, 1924 SOLVENT SOLVENT MIXING Y TANK SOLVENT AND OILY ewes AND OILY ACIDS 9 CENTRlFUG-AL l 13 MIXER .ZZ

CENTRWUGE.

Patented dune lb, 1930 DAVID 1. DAY, J5 WASHINGTUN, DISTRICT OF COLUMBIA; FRED J. GOBLE ADMINIS:

TRATOR OF SAID DAVID '1. DAY, DECEASED PROCESS FOR OBTAINING- NIGOTINE CARBOLATES FROM CRUDE SHAME OIL Application filed November lhis invention relates to a new and useful process for the treatment of crude shale oil, and particularly contemplates a process for the extraction of the compounds of oily bases 5 and oily acids from crude shale oil by treating such oil with a solvent in which the oil is insoluble but in which said compounds are soluble.

It is known that shale-tars and lignite-tars have been treated with various solvents, chief among which are acetone and alcohol, for the purpose of obtaining parafiin and highly viscous lubricating oils and to free them from asphaltlike components. This treatment, however, has alwaysbeen confined to the tars and residues and therefore is not in any way similar to the process now disclosed. It is clearly recognized that shale oil will yield products which are different from, but not 2 necessarily inferior to, i the corresponding products from ordinary petroleum. The present process is initiated by directly treating crude shale oil with a solvent at the outset, without depending upon any resulting residues or tars.

The invention particularly contemplates a process which will efiectually remove practi-, cally all of the oily bases and oily acids from crude shale oil. It has resulted in a process by which large quantities of insecticides may be produced from a hitherto unknown source. The invention resides in the process to be more fully described hereinafter and the novelty of which will be particularly pointed out and claimed.

In order that the various steps of the process will be readily understood by those skilled in the art, reference is made to the accompanying drawing to illustrate one form 40 of apparatus which may be employed with advantage to perform the process.

Before describing'in detail the preferredmethod of carrying out the process as regards the ingredients and steps employed, the process may be briefly described as follows: Crude shale oil, such, for instance, as that obtained from California shale is mixed with ordinary.

alcohol, preferably a liquid monohydric alcohol. The two are mixed in equal volumes but 5 if the alcohol is heated to some extent, then 12, 1924. Serial No. 749,570.

the proportion of alcohol may be reduced. The oil and alcohol mixture is then thorough- 1y agitated during which step the alcohol utilizes its property of extracting the compounds of oily bases and oily acids. lit is to be noted that the oil is insoluble in the alcohol but the compounds contained in the oil are soluble in the alcohol. The mixture of oil and alcohol with the material which the alcohol now holds in solution, is directed to a suitable separating device which will separate out the oil and send it to an oil tank for use in any way desired. The alcohol and the material that it holds in solution will be conducted to a still which is heated for the purpose of driving off the alcohol as a vapor. This alcohol vapor is then condensed and the liquid alcohol may be returned to the alcohol tank for re-use upon further quantities of crude shale oil. The compounds of oily bases and oily acids settle to the bottom of the still and may be drawn ofi for use as de sired.

Among these compounds has been identified pyridine-carbolate as the carbolic acid has been isolated from the pyridine. The other members of the pyridine group are undoubtedly present, as evidenced by the fact that they boil at a higher temperature than the pyridine itself. The presence of nicotine carbolate has been well established by quantitative examinations made according to the method prescribed by the'Otficial Association of Agricultural Chemists for the determ1na tion of nicotine in the tobacco extracts.

The term cresylic acid has been used throughout this specification because it covers the-usual run of such acids as have been obtained by other authorities and investigators. Nicotine and other oily bases in oil are not free bases, but are combined with various organic oily acids which fall within the general class of cr esylic acids.

The compounds of oily bases and oily acids ggextracted from crude shale oil by this process bonstitute a new and extremely valuable mix ture of insecticides.

Having now described generally the process one example of performing the same in detail will be set forth, the same being devent is permitted to flow from the tank 4 through the pipe 5 into the mixing tank 3 now containing the. crude shale 'oil whereupon a mixture of oil and solvent results. The exact amount of alcohol that is necessary for the proper treatment of each quantity of oil depends on materials treated and on surrounding conditions. Practice has shown that when the oil and alcohol are mixed in equal volumes heating of the alcohol may be dispensed with and conversely, if the alcohol is heated to a certain extent, the proportion of alcohol may be reduced. The oil and solvent mixture is permitted to flow from the mixing tank through the pipe 6 to acentrifugal mixer 7, driven by a motor 8. The mixing tank 3 is never filled entirely because in such a case the oil would settle to the bottom of the tank and the alcohol would remain on the top and a proper mixture would not result as is the case when the mixture is permitted to flow continually from the tank.

The next step in the process consists in thoroughly mixing the oil and the solvent in the centrifugal mixer 7 and it is during this mixing step that the solvent utilizes its property of extracting the compounds of the oily bases and the oily acids. The mixture is thereupon directed through the pipe: 9 to the centrifuge 10 which may be of any desired type. The centrifuge is preferably driven by the same motor which serves to drive the centrifugal mixer 7.

The centrifuge effects a complete separation of the mixture, separating the oil which by means of (pipe 18 for use as insecticides. The extracte products are in a suificiently pure state and require no further treatment.

It is quite obvious that many forms of apparatus may be used to effect the process above setforth and it is to be understood that the particular arrangement illustrated represents but one form of apparatus which may be employed with advantage.

I claim:

1. The process of extracting the compounds of oily bases and oily acids from crude shale oil, which proces consists in comingling crude shale oil with solvent comprised of liquid monohydric cohol in which the oil is insoluble but 'n which said compounds of oily bases an oily acids are soluble and thus ef-- fecting the solution .of said compounds in said solvent, and recovering the oily bases and oily acids from said oil.

-2. The process of extracting the compounds of oily bases and oily acids from crude shale oil, which process consists in comingling crude shale oil with a solvent comprised of liquid monohydric alcohol in which the oilis insoluble but in which said compounds of oil bases and oily acids are soluble and thus e fecting the solution of said compounds in said solvent, subjecting the mixture of solvent with dissolved material and the insoluble oil to separating treatment to remove the .oil therefrom, and finally separating said previously contained the oily bases and'oily acids from the solution of solvent and oily bases and oily acids. The oil is drawn oif from the centrifuge through the pipe 11 and maybe used for any desirable purpose. The resultant solution, otherwise known as the mixture of the solvent and oily bases and oily' acids is conducted by means of pipe 12 to the still 13 which is heated by the heater 14.

The final'step comprises heating the resultant solutionin the still so "as to effect a complete volatilization of the solvent which is conducted in its vapor state through the pipe 15 to the condenser 16 where the vapor is condensed once more and is returned to the original solvent storage tank 4 by means of the pipe 17; for use again'in-t he treatment of fresh batches of oil.

The oily bases and oily acids which have settled to the bottom of the still are removed 

